Microencapsulated aqueous polymerization catalyst

ABSTRACT

The present invention discloses an aqueous polymerization medium comprising (1) a catalyst composition which contains (a) an organometallic compound and (b) a transition metal compound wherein said catalyst composition is microencapsulated in a polyene product; and (2) water. This invention also discloses an aqueous polymerization medium comprising (1) a catalyst composition which is prepared by dissolving in an inert organic solvent containing at least one polyene (a) a transition metal compound, and (b) an organometallic compound; and (2) water. This aqueous polymerization medium is very useful in the polymerization of unsaturated hydrocarbon monomers. It is of greatest value in the polymerization of conjugated diolefin monomers into stereo-regulated polymers. This invention reveals a very useful process for producing polybutadiene composed essentially of syndiotactic 1,2-polybutadiene in an aqueous medium comprising polymerizing 1,3-butadiene in said aqueous medium in the presence of (1) a catalyst composition microencapsulated in a polyene product which contains (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX.sub. n, wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 , wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms; and (2) carbon disulfide.

BACKGROUND OF THE INVENTION

The present invention discloses an aqueous polymerization mediumcomprising (1) a catalyst composition which contains (a) anorganometallic compound and (b) a transition metal compound wherein saidcatalyst composition is microencapsulated in a polyene product; and (2)water. This invention also discloses an aqueous polymerization mediumcomprising (1) a catalyst composition which is prepared by dissolving inan inert organic solvent containing at least one polyene (a) atransition metal compound and (b) an organometallic compound and (2)water. This aqueous polymerization medium is very useful in thepolymerization of unsaturated hydrocarbon monomers. It is of greatestvalue in the polymerization of conjugated diolefin monomers intostereo-regulated polymers. This invention reveals a very useful processfor producing a polybutadiene composed essentially of syndiotactic1,2-polybutadiene in an aqueous medium comprising polymerizing1,3-butadiene in said aqueous medium in the presence of (1) a catalystcomponent microencapsulated in a polyene product which contains (a) atleast one cobalt compound selected from the group consisting of (i)β-diketone complexes of cobalt, (ii) β-keto acid ester complexes ofcobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15carbon atoms, and (iv) complexes of halogenated cobalt compounds of theformula CoX_(n), wherein X represents a halogen atom and n represents 2or 3, with an organic compound selected from the group consisting oftertiary amine alcohols, tertiary phosphines, ketones andN,N-dialkylamides, and (b) at least one organoaluminum compound of theformula AlR₃ wherein R represents a hydrocarbon radical of 1 to 6 carbonatoms; and (2) carbon disulfide.

The syndiotactic 1,2-polybutadiene produced in accordance with thisinvention is valuable as the material of films, fibers, and many othershaped products, because of its unique properties such as high meltingpoint, high crystallinity and excellent solvent resistance. Furthermore,this syndiotactic 1,2-polybutadiene exhibits excellent mechanicalproperties, particularly impact strength, when crystallinity and meltingpoints are moderated.

The polybutadiene produced by the subject process possesses vinylradical side chains, and consequently shows remarkably improved surfacecharacteristics over those of polyolefin resins. Syndiotactic1,2-polybutadiene has a unique combination of properties which make itvery useful in tires. For example, both wear and rolling resistance areimproved by the inclusion of this polymer in tires.

The vinyl radical side chains present in this syndiotactic1,2-polybutadiene also conveniently allow for the post-treatment of thepolymer, such as, crosslinking, graft-polymerization, etc.

Methods for making this polymer by polymerization in hydrocarbons orhalogenated hydrocarbon solvents are well-known.

A process for the preparation of 1,2-polybutadiene which comprisespolymerizing 1,3-butadiene in the liquid phase, in the presence of acatalyst composition composed of:

(a) a cobalt compound

(b) an organoaluminum compound of the formula

    AlR.sub.3

in which R is a hydrocarbon radical of 1-6 carbons, and

(c) carbon disulfide is disclosed in U.S. Pat. No. 3,778,424, which isherein incorporated by reference in its entirety. U.S. Pat. No.3,901,868 reveals a process for producing a butadiene polymer consistingessentially of syndiotactic 1,2-polybutadiene by the successive stepsof:

(a) preparing a catalyst component solution by dissolving, in an inertorganic solvent containing 1,3-butadiene, a cobalt compound, soluble inthe organic solvent, such as (i) cobalt-β-diketone complex, (ii)cobalt-β-keto acid ester complex, (iii) cobalt salt of organiccarboxylic acid, and (iv) halogenated cobalt-ligand compound complex,and an organoaluminum compound,

(b) preparing a catalyst composition by mixing the catalyst componentsolution with an alcohol, ketone or aldehyde compound and carbondisulfide,

(c) providing a polymerization mixture containing desired amounts of1,3-butadiene, the catalyst composition and an inert organic solvent,and

(d) polymerizing 1,3-butadiene at a temperature of -20° C. to 90° C.This patent is herein incorporated by reference in its entirety.

U.S. Pat. No. 3,778,424 indicates that the presence of water in thecatalyst and/or the polymerization system reduces the polymer yield.U.S. Pat. No. 3,901,868 indicates that it is well-known that theorganoaluminum catalyst component should be prevented from contact withwater.

One aqueous polymerization of a stereo-regulated polymer of commercialsignificance should be noted. Polychloroprene is made in an aqueousemulsion with a free radical generating catalyst. This polymer has morethan 95 percent of its monomer units in a 1,4-configuration (mostlytrans). This structural purity is probably caused by steric andelectronic effects in the polymerizing chlorinated hydrocarbon monomers,but in any case is quite untypical of a polymer prepared in a freeradical polymerization. Some other exceptions to the general rule thatstereoregulated polymers can only be prepared in a nonaqueous mediuminclude the preparation of crystalline trans 1,4-polybutadiene which hasbeen synthesized in an aqueous medium employing certain metal salts,such as those of rhodium and ruthenium as the catalyst, and thepreparation of trans polyisoprene has also been synthesized in wateremploying a π-allyl nickel catalyst. 1,2-polybutadiene has been preparedin water using palladium salts as the catalyst. Low yields and otherpractical problems have discouraged the large scale use of these aqueouspolymerizations commercially.

Obviously, the synthesis of stereo-regulated polymers in an aqueoussuspension has important advantages over solution polymerization. Wateras a medium in which to carry out such a polymerization is lessexpensive, more easily purified, less sensitive to oxygen, and has ahigher heat capacity. Such an aqueous process can be carried out inemulsion-type reactors with little or no reactor modification. Theaqueous process also permits higher monomer and higher solidsconcentrations in the reactor because of the lower viscosity of apolymer suspension compared with a polymer solution.

Unfortunately, it has been the general rule that synthetic stereoregulated polymers can only be synthesized in solution processes.Aqueous processes have not been available in which there was anorganometallic catalyst component present.

SUMMARY OF THE INVENTION

Since water can decompose the organoaluminum catalyst component used inthe polymerization of syndiotactic 1,2-polybutadiene, it has beenbelieved that the removal of essentially all of the water from such apolymerization system was desirable. The present invention reveals atechnique for "protecting" such an organoaluminum catalyst componentfrom water which even allows for carrying out aqueous suspensionpolymerizations in a water medium.

This invention is useful in the polymerization of unsaturatedhydrocarbon monomers to polymers. It is particularly useful in thesynthesis of stereo regulated polymers from conjugated diolefinmonomers. Stereo regulated hydrocarbon polymers can be synthesized in anaqueous medium in the presence of a catalyst composition comprising (1)an organometallic and (2) a transition metal compound which ismicroencapsulated in a polyene product. Some representative examples ofconjugated diolefins that conceivably can be polymerized into stereoregulated polymers include isoprene, piperylene, butadiene, and thelike. The transition metal compounds that can be employed in thecatalyst composition include: β-diketone complexes of coablt: β-ketoacid ester complexes of cobalt; cobalt solids of organic carboxylicacids; complexes of halogenated cobalt compounds of the formula CoX_(n),wherein X represents a halogen atom and n represents 2 or 3, with anorganic compound; and the like. The organometallic compounds that can beemployed in the catalyst composition include: organoaluminum compoundsof the formula: AlR₃ ; organolithium compounds of the formula: LiR;organomagnesium compounds of the formula: MgR₂ and the like. Thepreferred organometallic compounds are the organoaluminum compounds ofthe formula: AlR₃ and the organolithium compounds of the formula: LiR.

These catalyst components are microencapsulated in at least one polyeneproduct in order to protect the catalyst from the water used as themedium in these polymerizations. It is believed that a hydrophobicshield is formed around the catalyst that the water cannot readilypenetrate. However, this hydrophobic shield or membrane is probablypermeable by the monomer being polymerized. The polyene product formed,that microencapsulates the catalyst, is believed to be either amonomeric complex, an oligomer of the polyene, or a polymer of thepolyene. This polyene product can be formed from the same monomer thatis being polymerized into a polymer in the main polymerization or from adifferent polyene that is not being used in the main polymerization ofthis invention. Polyenes are olefins that contain 2 or more doublebonds. A probable explanation of the effectiveness of microencapsulationor hydrophobic shielding of the catalyst is that the polyene productcomprises part of the ligand assemblage around the transition metal atomor atoms. The polyene may be bound to the metal, for example, by π-allylbonding which is inert to water because of both steric and chemicaleffects of the ligand assemblage. The bond between metal and polyene,however, is readily replaced by a new π-allyl bond between metal andincoming monomer molecule, which at the same time forms a sigma bond tothe displaced polyene. Then another molecule moves into repeat thisinsertion process. Continuation of the process builds up a polymermolecule.

The catalyst compositions used in this invention are microencapsulatedby employing a prereaction process. In this preparation process theorganometallic component and the transition metal compound component ofthe catalyst composition are dissolved in an inert organic solvent withat least one polyene monomer. The ratio of the monomer to the transitionmetal compound in this catalyst component solution should be at least1.0 and preferably about 25 by mole. This catalyst component solution ispreferably prepared at a temperature of 10° C. to 50° C. and preferablycontains 0.0005 to 1.0 percent by mole, more preferably 0.001 to 0.5percent by mole of the transition metal compound and 0.001 to 10 percentby mole and more preferably 0.03 to 5 percent by mole of theorganometallic compound based on the amount by mole of monomer that willbe polymerized in the main polymerization of this invention. Such acatalyst component solution can be added to water to form an aqueouspolymerization medium that is useful in the polymerization of monomersto polymers.

This invention discloses how a microencapsulated catalyst is able toproduce polymer while dispersed in water. For a givenorganometallic/transition metal catalyst to be effective forpolymerization in the presence of water, the water-sensitive catalystcomponents must be chosen and assembled in such a way that the catalystis encapsulated or shielded from water and yet accessible to monomer.More particularly, catalysts are described in this invention which areshielded from water and accessible to butadiene monomer so thatcrystalline syndiotactic 1,2-polybutadiene is produced in high yield.

POLYBUTADIENE SYNTHESIS PROCESS

The catalyst compositions of this invention which are microencapsulatedin a polyene product are of greatest value in the aqueous polymerizationof butadiene monomer into polybutadiene which is composed essentially ofsyndiotactic 1,2-polybutadiene. This invention discloses a process forproducing polybutadiene composed essentially of syndiotactic1,2-polybutadiene, comprising the steps of:

(A) preparing a catalyst component solution by dissolving, in an inertorganic solvent containing 1,3-butadiene (a) at least one cobaltcompound selected from the group consisting of (i) β-diketone complexesof cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobaltsalts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv)complexes of halogenated cobalt compounds of the formula CoX_(n),wherein X represents a halogen atom and n represents 2 or 3, with anorganic compound selected from the group consisting of tertiary aminealcohols, tertiary phosphines, ketones, and N,N-dialkylamides, and (b)at least one organoaluminum compound of the formula AlR₃, wherein Rrepresents a hydrocarbon radical of 1 to 6 carbon atoms;

(B) preparing a reaction mixture by mixing said catalyst componentsolution with a 1,3-butadiene/water mixture containing desired amountsof said 1,3-butadiene;

(C) preparing a polymerization mixture by mixing carbon disulfidethroughout said reaction mixture, and

(D) polymerizing said 1,3-butadiene in said polymerization mixture intopolybutadiene while agitating said polymerization mixture.

The polymer produced by the process of the present invention is composedessentially of syndiotactic 1,2-polybutadiene and generally has amelting point of 70° C. to 210° C. The crystallinity and melting pointof the polybutadiene produced by using this process can be controlled byadding hydrocarbon-soluble alcohols, ketones, nitriles, aldehydes oramides to the polymerization mixture.

In the first step of this synthesis of syndiotactic 1,2-polybutadiene, acatalyst component solution is prepared by dissolving at least onecobalt compound and at least one organoaluminum compound in an inertorganic solvent containing at least one polyene monomer dissolvedtherein.

The term "an inert organic solvent" used herein refers to an organicsolvent chemically inert to all of the catalyst components used in theprocess of the present invention, 1,3-butadiene and the butadienepolymer. Some representative examples of inert organic solvents includearomatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons,halogenated aromatic hydrocarbons, and mixtures of two or more of theabove-mentioned compounds. The aromatic hydrocarbons may be benzene,toluene, xylenes, ethylbenzene, diethylbenzene or isobutylbenzene; andthe aliphatic hydrocarbons may be n-hexane, isohexanes, n-heptane,n-octane, isooctanes, n-decane, 2,2-dimethylbutane, petroleum ether,kerosene, petroleum spirit or petroleum naphtha, and the alicyclichydrocarbon may be either cyclohexane or methylcyclohexane. Thehalogenated aromatic hydrocarbon may be chlorobenzene, dichlorobenzenesor trichlorobenzenes.

The cobalt compound usable for the process of the present invention issoluble in an inert organic solvent selected from the group consistingof

i. β-diketone complexes of cobalt;

ii. β-keto acid ester complexes of cobalt;

iii. cobalt salts of organic carboxylic acid having 1 to 25 carbonatoms, and

iv. complexes of halogenated cobalt compounds of the formula:

    CoX.sub.n

wherein X represents a halogen atom and n represents 2 or 3, with anorganic compound selected from the group consisting of tertiary amines,alcohols, tertiary phosphines, ketones and N,N-dialkylamides.

The β-diketone compound to form a complex with a cobalt atom is of theformula: ##STR1## wherein R¹ and R⁴, which are the same as or differentfrom one another, are an alkyl radical of 1 to 6 carbon atoms and R² andR³, which are the same as or different from one another, are a hydrogenatom or an alkyl radical having 1 to 6 carbon atoms. This type ofβ-diketone complex of cobalt may be cobalt (II) acetylacetonate orcobalt (III) acetylacetonate.

The β-keto acid ester to form a complex with a cobalt atom may be of theformula: ##STR2## wherein R¹, R², R³ and R⁴ are the same as definedabove. This type of cobalt complex may be a cobalt-acetoacetic acidethyl ester complex.

The cobalt salt of organic carboxylic acid may be either cobalt octoateor cobalt naphthenate.

In the ligand compounds capable of forming a complex with a halogenatedcobalt compound, the tertiary amine may be pyridine, triethylamine,tributylamine or dimethylaniline, the alcohol may be methyl alcohol orethyl alcohol, the tertiary phosphine may be trimethyl phosphine,tributyl phosphine or triphenyl phosphine, the ketone may be acetone ormethyl ethyl ketone and the N,N-dialkylamide may beN,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide orN,N-diethylacetamide. The complex of halogenated cobalt is preferablyeither a complex of cobalt chloride with pyridine or ethyl alcohol.

The organoaluminum compound usable for the process of the presentinvention is of the formula AlR₃ wherein R represents a hydrocarbonradical of 1 to 6 carbon atoms. They hydrocarbon radical may be analkyl, cycloalkyl or aryl radical of 1 to 6 carbon atoms. Preferably,the organoaluminum compound may be trimethylaluminum, triethylaluminumor triphenylaluminum.

In the preparation of the catalyst component solution, it is importantthat the cobalt compound and the organoaluminum compound are dissolvedin the inert organic solvent containing at least one polyene. Somepolyenes that can be used in the formation of the polyene products usedto prepare microencapsulated catalysts are 1,3-butadiene,1,3-pentadiene, isoprene, myrcene, and 1,5-cyclooctadiene. Polyenes inwhich at least two of the double bonds are conjugated and which haveminimal substitution on the double bonds are preferred, particularly1,3-butadiene. Other olefins which can be used are those which arecapable of serving as chelating agents for transition metals, such as1,5-cyclooctadiene. Polyenes with neither conjugation nor good chelatingpotential are much less effective. If the preparation is carried out inthe absence of a polyene, the resultant catalyst component solution isnot effective as a component of the catalyst composition of the presentinvention. The polyene is preferably used in a ratio by mole of at least1.0, more preferably, at least 5.0 to the amount by mole of the cobaltcompound to be used in the catalyst component solution. The preferredpolyenes for use in this invention are 1,3-butadiene, 1,3-pentadiene,isoprene, and myrcene. The most preferred polyene is 1,3-butadiene.

Generally, the larger the ratio of the amount of polyene to the cobaltcompound in the catalyst component solution, the higher the activity ofthe catalyst. However, the activity of the catalyst reaches a maximumvalue at a ratio by mole of polyene monomer to the cobalt compound usedin the catalyst component solution of between 10 and 200. For example,if a molar ratio of polyene monomer to the cobalt compound of 10,000 isemployed the activity of the catalyst will be similar to that of thecatalyst prepared from a catalyst component solution containing a ratioof polyene monomer to the cobalt compound of from 10 to 200. If theratio is less than 1.0, the resultant catalyst composition has pooractivity.

The catalyst component solution is preferably prepared at a temperatureof 10° to 50° C. and preferably contains 0.0005 to 1.0% by mole, morepreferably 0.001 to 0.5% by mole, of the cobalt compound. 0.001 to 10%by mole, more preferably, 0.03 to 5% by mole of the organoaluminumcompound based on the amount by mole of 1,3-butadiene to be polymerized.The ratio by mole of the organoaluminum compound to the cobalt compoundis preferably in a range from 0.5 to 50, more preferably, from 0.2 to10.

In the preparation of the catalyst component solution it is preferredfor the cobalt compound to be first dissolved in the inert organicsolvent in the presence of the polyene monomer and then for theorganoaluminum compound to be added to the solution. However, verysatisfactory results can also be obtained when the organoaluminumcompound is added first.

In the preparation of this catalyst component solution theorganoaluminum compound should not be allowed to come in contact withwater. This is because water can completely decompose suchorganoaluminum compounds. Accordingly, it is preferable that the inertorganic solvent to be used to prepare the catalyst component solution bepreliminarily dehydrated at least up to a content of water which isinsufficient to completely decompose the entire amount of theorganoaluminum compound.

It is preferable that the catalyst component solution be prepared usinga dehydrated inert organic solvent. However, a trace of water in theinert organic solvent can be present up to a concentration of about 500ppm (parts per million by weight). In fact, it is believed that thetotal elimination of water from such a catalyst component solution isundesirable. It is preferred for no more than 200 ppm of water to bepresent in the inert organic solvent used in the preparation of thecatalyst component solution. If the content of water in the inertorganic solvent is larger than 500 ppm, the catalyst component solutionhas to contain a relatively large amount of the cobalt compound andorganoaluminum compound. This results in an economic disadvantage. If asufficient amount of water is present in the inert organic solvent usedin the preparation of the catalyst component solution the catalyst canbe completely destroyed.

It is desirable to allow the prereaction used in the preparation of thecatalyst component solution to run for a period of at least 30 seconds,and more preferably for at least 1 minute before mixing the catalystcomponent solution with the 1,3-butadiene/water mixture to form thereaction mixture. Longer time periods can be used without the catalystcomponent solution losing its activity.

After the organoaluminum compound has been incorporated in the catalystcomponent solution using the above-described technique the catalyst is"protected" from decomposition by water. This is believed to be due to amicroencapsulation of the catalyst by polyene product formed in theprereaction process used in the preparation of the catalyst componentsolution.

It is believed that a hydrophobic shield is formed around the catalystthat water cannot readily penetrate; however, this hydrophobic shield ormembrane is probably permeable by the butadiene monomer beingpolymerized into the syndiotactic 1,2-polybutadiene. When 1,3-butadieneis used as the polyene, the butadiene product which microencapsulatesthe catalyst is believed to be a butadiene monomer complex, anoligomerized butadiene or a polymer of butadiene. It has been determinedthat this protection is sufficient to allow for the use of this catalystcomponent solution in an aqueous suspension polymerization of butadieneinto 1,3-polybutadiene of syndiotactic crystallinity.

In the second step of this process a reaction mixture is prepared bymixing the catalyst component solution with a 1,3-butadiene/watermixture. This 1,3-butadiene/water mixture can contain from as little asabout 2% butadiene to as much as about 50% butadiene by weight. It ispreferred for this 1,3-butadiene/water mixture to contain from 15% to35% by weight butadiene and it is more preferred for it to contain about20 to 25% butadiene by weight. Since 1,3-butadiene is very volatile itwill be necessary to prepare this mixture in a closed system. Agitationshould be provided in the preparation of the reaction mixture in orderto insure that the catalyst component solution and 1,3-butadiene aredistributed essentially homogeneously throughout the mixture. Since1,3-butadiene is essentially insoluble in water it will be present inthis mixture in the form of droplets which are distributed throughoutthe mixture. If agitation is discontinued there will be a separation ofthe organic and aqueous components of this mixture into two layers. Theorganic and aqueous layers of this reaction mixture can be mixedtogether again by agitating the reaction mixture.

In the third step of this process a polymerization mixture is preparedby mixing carbon disulfide throughout the above-described reactionmixture. The amount of carbon disulfide that can be added will varybetween 0.005 mole percent and 2 mole percent based on the amount ofmoles of 1,3-butadiene to be polymerized in the polymerization mixture.More preferably the amount of carbon disulfide added will vary between0.001 and 1 mole percent based on the amount of moles of 1,3-butadieneto be polymerized in the polymerization mixture.

In the process of the present invention, the larger the proportion ofthe carbon disulfide in a range from about 0.0005 to about 0.5% by molebased on the amount by mole of the 1,3-butadiene to be polymerized inthe polymerization mixture, the larger the yield of the polymer productobtained from the polymerization mixture. However, too large an amountof carbon disulfide, for example, larger than 0.5% by mole, causes adecrease in the polymer yield.

In the process of the present invention the crystallinity and meltingpoint of the polybutadiene produced can be controlled by addingalcohols, ketones, nitriles, aldehydes, or amides to the polymerizationmixture. In this aqueous suspension polymerization process there is alimitation of controlling crystallinity and melting point with agentswhich are water-soluble. Thus ethanol and methanol are not as effectiveas other alcohols which are much less soluble in water than inhydrocarbons. Water soluble agents can not be used effectively tocontrol crystallinity and melting point (only hydrocarbon soluble agentscan be used). A detailed description of the agents and techniques thatare used to control crystallinity and melting points is given in U.S.Pat. Nos. 3,901,868 and 4,153,767. These patents are incorporated hereinby reference in their entirety. As has been pointed out, water solubleagents, such as ethanol and methanol, are not effective agents. Otheralcohols such as, 2-ethyl-1-hexanol, 1-decanol, and 5-tridecanol, whichare not soluble in water, have been used very successfully.

In the final step of this process the 1,3-butadiene monomer in thepolymerization mixture is converted into polybutadiene while agitatingthe polymerization mixture. If the use of an antioxidant is desired, itmay be added conveniently at the beginning of the polymerization. Thispolymerization of 1,3-butadiene monomer can be carried out at atemperature from about -20° C. to about 90° C. It is preferable for thepolymerization temperature to be from 0° C. to 40° C. The most preferredpolymerization temperature is about 10° C. At temperatures below 0° C.an antifreeze agent can be added to the polymerization mixture to keepit from freezing.

This polymerization can be carried out either under a normal pressure orin a pressurized system. This polymerization can be carried out under anitrogen atmosphere with good results. Such a polymerization can be runfor a period of from about 1 to about 30 hours. It is generallypreferred for the polymerization to be run for about 10 hours. However,the optimum polymerization time will vary greatly with thepolymerization temperature, catalyst, the amount of catalyst used, etc.The polybutadiene formed using the process of this invention will floatto the surface of the polymerization mixture and can easily berecovered.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Various embodiments of the process of the present invention in practiceare illustrated by the following working examples. These examples areintended merely to illustrate the present invention and not in any senseto limit the scope in which the present invention can be practiced.Unless specifically indicated otherwise, parts and percentages are givenby weight.

EXAMPLE 1

A typical polymerization utilizing the process of this invention wascarried out by preparing a 1.85 M (molar) solution of butadiene inhexane under a nitrogen atmosphere. 22.5 ml (milliliters) of thissolution was added to a 4 oz (118 ml) bottle. 5.53 ml of a 1.52 Mtriethylaluminum in hexane solution was added to the bottle. 1.74 ml ofa 0.96 M solution of cobalt octoate in mineral spirits was then added.The bottle was then placed on a shaker for a period of about one hour atroom temperature in order to form the catalyst component solution.

A reaction mixture was prepared by adding 0.58 ml of the aforementionedcatalyst component solution to a 4 oz (118 ml) bottle containing 40grams of deionized water and 20 grams of 1,3-butadiene monomer. Thepolymerization mixture was then prepared by adding 0.49 ml of a 0.10 Msolution of carbon disulfide in hexane to the aforementioned reactionmixture. The bottle was then placed in a constant temperature bath andtumbled at 10° C.

After the polymerization was run for a period of 22 hours the bottle wasremoved from the constant temperature bath. The polybutadiene that wasobtained was then soaked in 300 ml of a 1 percent solution of2,6-di-tert-butyl-p-cresol in methanol. The polybutadiene was washed twotimes with such a methanol solution and it was then filtered off andvacuum dried at 90° C. The yield of polymer was determined to be 38percent. Using differential scanning calorimetry, the peak meltingtemperature was found to be 188° C.

EXAMPLE 2

The procedure specified in Example 1 was utilized in the synthesis of apolybutadiene except that 1.0 ml of 5-tridecanol was added to thereaction mixture after the triethylaluminum and cobalt octoate wereadded. The yield of polybutadiene was determined to be 63 percent andits melting point was 164° C. This shows that the addition of a waterinsoluble alcohol to the reaction mixture used in such a polymerizationcan reduce the melting point of the polybutadiene produced and increasethe yield. The melting point of the polybutadiene produced in such apolymerization can be accurately controlled by adjusting the amount ofalcohol present in the reaction mixture.

EXAMPLES 3 THROUGH 9

A catalyst component solution was prepared by adding 5.53 ml of a 1.52 Mtriethylaluminum in hexane solution to 22.5 ml of a 1.85 M butadiene incyclohexane solution which was in a 118 ml bottle under nitrogen,followed by the addition of 0.80 ml of a 2.09 M cobalt octoate inmineral spirits solution. This bottle was capped and placed on a shakerfor about one hour.

A series of reaction mixtures were prepared by adding various amounts ofthe aforementioned catalyst component solution to a series of 118 mlbottles containing 40 g of deionized water and 20 gram of 1,3-butadienemonomer. The amount of catalyst component solution added is shown inTable I. Various amounts (shown in Table I) of a 0.1 M carbon disulfidein cyclohexane solution were then added to the series of bottles to formpolymerization mixtures.

The bottles were placed in a constant temperature bath at 10° C. andtumbled for 20 hours. The polymers obtained were washed in a 1% solutionof 2,6-ditertiarybutyl-p-cresol in methanol and dried in a 65° C. forcedair oven for 10 hours. Polymer yields were determined and are shown inTable I. The peak melting temperature in Examples 3,4 and 6 wasdetermined to be 199° C. and was determined to be 200° C. in Example 5.

                  TABLE I                                                         ______________________________________                                               Catalyst Component                                                                            CS.sub.2 Solution                                                                        Polymer                                     Example                                                                              Solution Added (ml)                                                                           Added (ml) Yield                                       ______________________________________                                        3      0.56            0.49        46%                                        4      0.84            0.74        76%                                        5      1.12            0.98        96%                                        6      1.40            1.22       100%                                        7      1.68            1.47       100%                                        8      1.96            1.72       100%                                        9      2.24            1.96       100%                                        ______________________________________                                    

EXAMPLES 10 THROUGH 12

The same procedure that was specified in Example 2 was employed exceptthat various amounts of 1-butanol were used in these Examples in placeof the 5-tridecanol and the polymerization time was 25 hours. The amountof 1-butanol used and the resulting polymer yields, and peak meltingpoints as determined by differential scanning calorimetry are shown inTable II.

                  TABLE II                                                        ______________________________________                                        1-Butanol                                                                     Added (ml) Polymer Yield                                                                             Melting Temperature                                    ______________________________________                                        1.0        63%         177° C.                                         4.0        75%         140° C.                                         10.0       74%         116° C.                                         ______________________________________                                    

EXAMPLES 13 THROUGH 18

Six different polyenes were tested in a series of experiments toascertain their usefulness in the preparation of catalyst componentsolutions. 50 ml of a polyene in toluene solution of one of the polyeneslisted in Table III was added to a series of 118 ml bottles undernitrogen. 1.6 ml of a 2 M solution of cobalt octoate in mineral spiritsand 9.0 ml of a 1.52 M solution of triethylaluminum in hexane were addedto the bottles to produce a series of catalyst component solutions.

1.5 ml of these catalyst component solutions were added to a series of118 ml bottles containing 50 g of deionized water and 25 g of1,3-butadiene. 0.6 ml of a 0.2 M solution of a carbon disulfide inhexane was then added to the bottles to produce a series ofpolymerization mixtures. 0.032 millimoles of cobalt octoate, 0.128millimoles of triethylaluminum, and 0.032 millimoles of carbon disulfideper 100 g of 1,3-butadiene monomer were present in these polymerizationmixtures.

This series of bottles was then placed in a constant temperature bath at10° C. and tumbled for 20 hours. The contents of these bottles were thenpoured into a series of beakers containing 300 ml of methanol. Thepolymers produced were isolated by filtration, washed with water, anddried. The polyenes employed, the amount of the polyene employed, andthe polymer yields are shown in Table III.

                  TABLE III                                                       ______________________________________                                                             Amount of                                                Example  Polyene     Polyene*  Polymer Yield                                  ______________________________________                                        13       Isoprene    20        67                                             14       Myrcene     15        33                                             15       trans-      10        76                                                      Piperylene                                                           16       1,5-Cyclo-  20        22                                                      octadiene                                                            17       1-Pentene   22         0                                             18       Cyclooctene 38         0                                             ______________________________________                                         *in millimoles per 100 g of 1,3butadiene                                 

While certain representative embodiments and details have been shown forthe purpose of illustrating the invention, it will be apparent to thoseskilled in this art that various changes and modifications can be madetherein without departing from the scope of this invention.

What is claimed is:
 1. A process for producing polybutadiene composedessentially of syndiotactic 1,2-polybutadiene in an aqueous mediumcomprising polymerizing 1,3-butadiene in said aqueous medium in thepresence of (1) a catalyst composition which contains (a) at least onecobalt compound selected from the group consisting of (i) β-diketonecomplexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii)cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms,and (iv) complexes of halogenated cobalt compounds of the formulaCoX_(n), wherein X represents a halogen atom and n represents 2 or 3,with an organic compound selected from the group consisting of tertiaryamine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and(b) at least one organoaluminum compound of the formula AlR₃ wherein Rrepresents a hydrocarbon radical of 1 to 6 carbon atoms, wherein saidcatalyst composition is microencapsulated in a polyene product; and (2)carbon disulfide.
 2. A process for producing polybutadiene composedessentially of syndiotactic 1,2-polybutadiene in an aqueous mediumcomprising polymerizing 1,3-butadiene in said aqueous medium in thepresence of (1) a catalyst component solution which is prepared bydissolving in an inert organic solvent containing at least one polyene(a) at least one cobalt compound selected from the group consisting of(i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes ofcobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15carbon atoms, and (iv) complexes of halogenated cobalt compounds of theformula CoX_(n), wherein X represents a halogen atom and n represents 2or 3, with an organic compound selected from the group consisting oftertiary amine alcohols, tertiary phosphines, ketones andN,N-dialkylamides, and (b) at least one organoaluminum compound of theformula AlR₃ wherein R represents a hydrocarbon radical of 1 to 6 carbonatoms; and (2) carbon disulfide.
 3. A process for producingpolybutadiene composed essentially of syndiotactic 1,2-polybutadiene inan aqueous medium comprising polymerizing 1,3-butadiene in said aqueousmedium, distributing throughout said aqueous medium containing1,3-butadiene, a catalyst composition which contains (a) at least onecobalt compound selected from the group consisting of (i) β-diketonecomplexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii)cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms,and (iv) complexes of halogenated cobalt compounds of the formulaCoX_(n), wherein X represents a halogen atom and n represents 2 or 3,with an organic compound selected from the group consisting of tertiaryamine alcohols, tertiary phosphines, ketones and N,N-dialkylamides, and(b) at least one organoaluminum compound of the formula AlR₃ wherein Rrepresents a hydrocarbon radical of 1 to 6 carbon atoms wherein saidcatalyst composition is microencapsulated in a polyene product; followedby the distribution of carbon disulfide throughout said medium.
 4. Aprocess for producing polybutadiene composed essentially of syndiotactic1,2-polybutadiene in an aqueous medium comprising polymerizing1,3-butadiene in said aqueous medium by distributing throughout saidaqueous medium containing said 1,3-butadiene, a catalyst componentsolution which is prepared by dissolving in an inert organic solventcontaining at least one polyene (a) at least one cobalt compoundselected from the group consisting of (i) β-diketone complexes ofcobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt saltsof organic carboxylic acids having 6 to 15 carbon atoms, and (iv)complexes of halogenated cobalt compounds of the formula CoX_(n),wherein X represents a halogen atom and n represents 2 or 3, with anorganic compound selected from the group consisting of tertiary aminealcohols, tertiary phosphines, ketones and N,N-dialkylamides, and (b) atleast one organoaluminum compound of the formula AlR₃ wherein Rrepresents a hydrocarbon radical of 1 to 6 carbon atoms; followed by thedistribution of carbon disulfide throughout said medium.
 5. A processfor producing polybutadiene composed essentially of syndiotactic1,2-polybutadiene, comprising the steps of:(A) preparing a catalystcomponent solution by dissolving, in an inert organic solvent containing1,3-butadiene, (a) at least one cobalt compound selected from the groupconsisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid estercomplexes of cobalt, (iii) cobalt salts of organic carboxylic acidshaving 6 to 15 carbon atoms, and (iv) complexes of halogenated cobaltcompounds of the formula CoX_(n), wherein X represents a halogen atomand n represents 2 or 3, with an organic compound selected from thegroup consisting of tertiary amine alcohols, tertiary phosphines,ketones and N,N-dialkylamides, and (b) at least one organoaluminumcompound of the formula AlR₃ wherein R represents a hydrocarbon radicalof 1 to 6 carbon atoms; (B) preparing a reaction mixture by mixing saidcatalyst component solution with a 1,3-butadiene/water mixturecontaining desired amounts of said 1,3-butadiene; (C) preparing apolymerization mixture by mixing carbon disulfide throughout saidreaction mixture; and (D) polymerizing said 1,3-butadiene in saidpolymerization mixture into polybutadiene while agitating saidpolymerization mixture.
 6. A process as specified in claim 5 wherein theprocess of polymerizing said 1,3-butadiene is carried out at atemperature of from about -20° C. to about 90° C.
 7. A process asspecified in claim 6 wherein the process of polymerizing said1,3-butadiene is carried out at a temperature of from 0° C. to 40° C. 8.A process as specified in claim 7 wherein the process of polymerizingsaid 1,3-butadiene is carried out at a temperature of about 10° C.
 9. Aprocess as specified in claim 5 wherein said inert organic solvent isselected from the group consisting of aromatic hydrocarbons, aliphatichydrocarbons, alicyclic hydrocarbons, halogenated aromatic hydrocarbons,and mixtures of two or more of the above-mentioned compounds.
 10. Aprocess as specified in claim 5 wherein said catalyst component solutionis prepared by first dissolving said cobalt compound into said inertorganic solvent containing 1,3-butadiene and secondly, dissolving saidorganoaluminum compound into said inert organic solvent containing said1,3-butadiene and said cobalt compound.
 11. A process as specified inclaim 5 wherein said catalyst component solution contains 0.0005 to 1.0%by mole of said cobalt compound and 0.001 to 10% by mole of saidorganoaluminum compound, based on the amount by mole of said1,3-butadiene to be polymerized in said polymerization mixture.
 12. Aprocess as specified in claim 11 wherein said catalyst componentsolution contains 0.001 to 0.5% by mole of said cobalt compound and 0.03to 5% by mole of said organoaluminum compound, based on the amount bymole of said 1,3-butadiene to be polymerized in said polymerizationmixture.
 13. A process as specified in claim 5 wherein saidpolymerization mixture contains from 0.005 to 2 mole percent carbondisulfide, based on the amount by mole of said 1,3-butadiene to bepolymerized in said polymerization mixture.
 14. A process as specifiedin claim 13 wherein said polymerization mixture contains from 0.001 to 1mole percent carbon disulfide, based on the amount by mole of said1,3-butadiene to be polymerized in said polymerization mixture.
 15. Aprocess as specified in claim 5 wherein said catalyst component solutionis prepared at a temperature of 10° to 50° C.
 16. A process as specifiedin claim 5 wherein the ratio by mole of said 1,3-butadiene to saidcobalt compound in the catalyst component solution is about
 25. 17. Aprocess as specified in claim 16 wherein the ratio by mole of said1,3-butadiene to said cobalt compound in the catalyst component solutionis at least
 5. 18. A process as specified in claim 5 wherein the ratioby mole of the amount of said organoaluminum compound to said cobaltcompound is in the range from 0.5 to
 50. 19. A process as specified inclaim 18 wherein said ratio by mole of the amount of said organoaluminumcompound to said cobalt compound is from 2 to
 10. 20. A process asspecified in claim 5 wherein the 1,3-butadiene/water mixture containsfrom about 2% of about 50% 1,3-butadiene by weight.
 21. A process asspecified in claim 20 wherein the 1,3-butadiene/water mixture containsfrom 15% to 35% 1,3-butadiene by weight.
 22. A process as specified inclaim 21 wherein the 1,3-butadiene/water mixture contains about 20% to25% 1,3-butadiene by weight.
 23. A process as specified in claim 5wherein said inert organic solvent contains at most 500 ppm of waterbased on the weight of said inert organic solvent.
 24. A process asspecified in claim 23 wherein said amount of water is at most 200 ppmbased on the weight of said inert organic solvent.
 25. A process asspecified in claim 5 wherein said β-diketone complex of cobalt is amember selected from the group consisting of cobalt (II) acetylacetoneand cobalt (III) acetylacetonate.
 26. A process specified in claim 5wherein said β-diketone complex of cobalt has a diketone group of theformula: ##STR3## wherein R¹ and R⁴, which are the same as or differentfrom one another, are each an alkyl radical of 1 to 6 carbon atoms andR² and R³, which are the same as or different from one another, are eacha hydrogen atom or an alkyl radical having 1 to 6 carbon atoms.
 27. Aprocess as specified in claim 5, wherein said β-keto acid ester complexof cobalt has a β-keto acid ester group of the formula: ##STR4## whereinR¹, R², R³ and R⁴ are the same as defined above.
 28. A process asspecified in claim 5 wherein said β-keto acid ester complex of cobalt isa cobalt-acetoacetic acid ethyl ester complex.
 29. A process asspecified in claim 5 wherein said cobalt salt is either cobalt octoateor cobalt napthenate.
 30. A process as specified in claim 5 wherein saidorganoaluminum compound is selected from the group consisting oftrimethylaluminum, triethylaluminum, tributylaluminum andtriphenylaluminum.
 31. A process as specified in claim 1 or 3 whereinsaid polyene product is a product of at least one polyene selected fromthe group consisting of butadiene, 1,3-pentadiene, isoprene, andmyrcene.
 32. A process as specified in claim 2 or 4 wherein said polyeneis selected from the group consisting of butadiene, 1,3-pentadiene,isoprene and myrcene.
 33. A process as specified in claim 1 or 3 whereinsaid polyene product is a product of a conjugated polyene.
 34. A processas specified in claim 2 or 4 wherein said polyene is a conjugatedpolyene.